The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homorotaxane, built from a perylenediimide diimidazolium rod that threads two pillararene macrocycles, and a heterorotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combination of techniques including electron diffraction crystallography in the case of the heterorotaxane. Cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy are employed to establish the behaviour of the redox states of both rotaxanes and these data are used to inform photophysical studies using time-resolved infra-red (TRIR) and transient absorption (TA) spectroscopies. The latter studies illustrate the formation of a symmetry-breaking charge-separated state in the case of the homorotaxane in which charge transfer between the pillararene and perylenediimide is observed involving only one of the two macrocyclic components. In the case of the heterorotaxane charge separation is observed involving only the BN38C10 macrocycle and the perylenediimide leaving the pillararene components unperturbed.
Bibliographical noteFunding Information:
NRC gratefully acknowledges the support of the UK Engineering and Physical Sciences Research Council (EP/S002995/1). We acknowledge Diamond Light Source for time on Beamline I19 under Proposal CY21755.
© 2022, The Author(s).
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Physics and Astronomy(all)